CN114921122A - UV-curable iodine-resistant matte coating - Google Patents
UV-curable iodine-resistant matte coating Download PDFInfo
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- CN114921122A CN114921122A CN202210594141.5A CN202210594141A CN114921122A CN 114921122 A CN114921122 A CN 114921122A CN 202210594141 A CN202210594141 A CN 202210594141A CN 114921122 A CN114921122 A CN 114921122A
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- iodine
- curable
- agent
- matte coating
- solid product
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- 239000011630 iodine Substances 0.000 title claims abstract description 53
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 53
- 238000000576 coating method Methods 0.000 title claims abstract description 51
- 239000011248 coating agent Substances 0.000 title claims abstract description 48
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002775 capsule Substances 0.000 claims abstract description 39
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 35
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 16
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000003973 paint Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 239000011737 fluorine Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 34
- 239000012071 phase Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000012265 solid product Substances 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000003921 oil Substances 0.000 claims description 20
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 17
- 229930003268 Vitamin C Natural products 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 235000019154 vitamin C Nutrition 0.000 claims description 17
- 239000011718 vitamin C Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 8
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- -1 perfluoroalkyl mercaptan Chemical compound 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 3
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- KUDUQBURMYMBIJ-UHFFFAOYSA-N ethylene glycol diacrylate Substances C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- DKKXSNXGIOPYGQ-UHFFFAOYSA-N diphenylphosphanyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(C=1C=CC=CC=1)C1=CC=CC=C1 DKKXSNXGIOPYGQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 28
- 239000000843 powder Substances 0.000 abstract description 12
- 238000003848 UV Light-Curing Methods 0.000 abstract description 5
- 239000000945 filler Substances 0.000 abstract description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical group [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 101000663001 Mus musculus TNFAIP3-interacting protein 1 Proteins 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- SEUSOVWCZAOSEI-UHFFFAOYSA-N diphenoxyphosphanyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=C(C(=O)P(OC2=CC=CC=C2)OC2=CC=CC=C2)C(=CC(=C1)C)C SEUSOVWCZAOSEI-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FJQXCDYVZAHXNS-UHFFFAOYSA-N methadone hydrochloride Chemical compound Cl.C=1C=CC=CC=1C(CC(C)N(C)C)(C(=O)CC)C1=CC=CC=C1 FJQXCDYVZAHXNS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a UV-cured anti-iodine matte coating, which relates to the technical field of coatings, and comprises the following components in parts by weight: 20-30 parts of acrylic resin; 10-20 parts of active monomer; 30-60 parts of fluorine-containing carbon chain capsule type reducing agent; 3-8 parts of an initiator; 0.1-0.5 part of leveling agent; 0.1-0.5 part of dispersant; 0.1-0.5 part of defoaming agent. According to the UV curing iodine-resistant matte coating provided by the invention, firstly, the capsule type reducing agent has the capability of reducing iodine, and long fluorocarbon chains among capsules are mutually wound, so that the improvement of the iodine-resistant effect is facilitated; secondly, the long fluorocarbon chains on the surface of the capsule type reducing agent can be utilized, so that the capsule type reducing agent containing fluorocarbon chains floats on the surface of a paint film to form a concave-convex interface, the diffuse reflection effect is increased, the glossiness is further reduced, and the matte effect is realized on the premise of not increasing matte powder and fillers.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a UV-cured iodine-wine-resistant matte coating.
Background
Iodine has very strong permeability to ordinary PVC coiled material, once PVC coiled material is infected with iodine and just difficult clearance, seriously influences the cleanness and the pleasing to the eye of floor surface. The technical scheme is that an antioxidant is added into a UV coating, iodine is consumed by an oxidation-reduction method, or the iodine is prevented from permeating by improving the crosslinking density, but the method can only be used in a bright system with less filler, and for a matte system with more filler and matte powder, the iodine-resistant effect of the UV coating of the matte system is difficult to improve due to the adsorbability of powder, and the iodine-resistant effect is poor.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to solve the problem of poor iodine-containing effect of a UV coating of a matte system in the prior art, the invention provides the UV-cured iodine-containing matte coating, the floating type capsule type reducing agent is added into the UV-cured iodine-containing matte coating, the long fluorocarbon chains on the surfaces of the capsules float on the surface of a paint film to form a concave-convex interface, the diffuse reflection effect is increased, the glossiness is further reduced, meanwhile, the long fluorocarbon chains among the capsules are mutually wound, the surface tension is reduced, the penetration of iodine-containing wine can be blocked, the capsules have the function of reducing iodine-containing wine, and under the multiple protection effect, the matte coating can play an excellent iodine-containing effect and solve the problem of poor iodine-containing effect of the UV coating of the matte system in the prior art.
The technical scheme adopted by the invention for solving the technical problem is as follows:
the UV-cured iodine-alcohol-resistant matte coating comprises the following components in parts by weight:
alternatively, the fluorine-containing carbon chain capsule type reducing agent is prepared by the following method:
s1: adding an emulsifier into the vitamin C aqueous solution, and adjusting the pH value to 2-5 to form an aqueous phase;
s2: mixing hydroxyethyl methacrylate and trimethylolpropane triacrylate to form an oil phase;
s3: mixing the water phase and the oil phase, adding an initiator, stirring to form an emulsion, standing at 80 ℃ under an inert gas atmosphere for reaction, and then performing centrifugal separation, washing and drying to obtain a solid product A with the surface rich in-OH;
s4: mixing deionized water, a silane coupling agent and ethanol, adjusting the pH value to 3-6, adding the solid product A, stirring and reacting at 60 ℃ under the protection of inert gas, and then carrying out centrifugal separation, washing and drying to obtain a solid product B with the surface grafted with the silane coupling agent;
s5: mixing the solid product B, a catalyst 1173 and toluene, heating to 50 ℃, dropwise adding perfluoroalkyl mercaptan under the protection of inert gas, stirring and irradiating by using an LED lamp with the wavelength of 365nm, monitoring the reaction through FTIR measurement, and after a double bond absorption peak in a reactant disappears, centrifugally separating, washing and drying a reaction solution to obtain the fluorine-containing carbon chain capsule type reducing agent.
Optionally, the mass fraction of the vitamin C aqueous solution in step S1 is 30%; the mass fraction of the emulsifier in the vitamin C water solution is 5%.
Optionally, in step S2, the mass ratio of the hydroxyethyl methacrylate to the trimethylolpropane triacrylate is 3: 1.
Optionally, the mass ratio of the water phase to the oil phase in step S3 is 1: 5; the initiator accounts for 4% of the mass fraction of the oil phase.
Optionally, in the step S4, the mass ratio of the deionized water to the silane coupling agent to the ethanol is 2:1: 5; the volume of the solid product A is 1/4 of a mixed solution formed by the deionized water, the silane coupling agent and the ethanol.
Optionally, the mass-to-volume ratio of the solid product B to the toluene in step S5 is 1: 2.
Optionally, the acrylic resin is selected from at least one of epoxy modified acrylic resin, polyurethane modified acrylic resin, polyester modified acrylic resin and organic silicon modified acrylic resin.
Optionally, the reactive monomer is selected from at least one of pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, 1, 6-ethylene glycol diacrylate, tripropylene glycol diacrylate.
Optionally, the leveling agent is an organic silicon leveling agent; the defoaming agent is an organic silicon defoaming agent or a polyether defoaming agent; the dispersing agent is a macromolecular dispersing agent; the initiator is at least one selected from 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethyl benzoyl diphenylphosphine and 4-chlorobenzophenone.
The beneficial effects of the invention are:
according to the UV curing iodine-resistant matte coating provided by the invention, the reducing agent is designed into a capsule type structure, and the long fluorocarbon chains are grafted on the surface of the capsule type reducing agent, firstly, the capsule type reducing agent has the capability of reducing iodine, and the long fluorocarbon chains among the capsules are mutually wound, so that the surface tension of the coating is favorably reduced, the penetration of iodine can be blocked, certain antifouling property is realized, and the iodine-resistant effect is favorably improved; secondly, can utilize the long fluorine carbon chain on capsule type reductant surface for fluorine carbon chain capsule type reductant floats on the paint film surface, forms unsmooth interface, increases the diffuse reflection effect, and then reduces the glossiness, under the prerequisite that need not to increase matt powder and filler, realizes matt effect, avoids leading to the anti iodine wine effect of UV coating of matt system to be difficult to promote because of the adsorptivity of powder, and then through the mutual synergistic effect of multiple protection efficiency, makes this matt coating can have excellent anti iodine wine efficiency.
Detailed Description
The present invention will now be described in further detail. The embodiments described below are exemplary and are intended to be illustrative of the present invention and should not be construed as limiting the present invention, and all other embodiments that can be obtained by one of ordinary skill in the art based on the embodiments of the present invention without inventive step fall within the scope of the present invention.
In order to solve the problem that the UV coating of a matte system in the prior art is poor in iodine-containing wine resistant effect, the invention provides a UV curing iodine-containing wine resistant matte coating which comprises the following components in parts by weight:
according to the UV-cured iodine-resistant matte coating provided by the invention, the reducing agent is designed into a capsule structure, and the long fluorocarbon chains are grafted on the surface of the capsule reducing agent, firstly, the capsule reducing agent has the capability of reducing iodine, and the long fluorocarbon chains among the capsules are mutually wound, so that the tension on the surface of the coating is favorably reduced, the penetration of iodine can be blocked, certain anti-pollution performance is realized, and the iodine-resistant effect is favorably improved; secondly, can utilize the long fluorine carbon chain on capsule type reductant surface for fluorine carbon chain capsule type reductant floats on the paint film surface, forms unsmooth interface, increases the diffuse reflection effect, and then reduces the glossiness, under the prerequisite that need not to increase matt powder and filler, realizes matt effect, avoids leading to the anti iodine wine effect of UV coating of matt system to be difficult to promote because of the adsorptivity of powder, and then through the mutual synergistic effect of multiple protection efficiency, makes this matt coating can have excellent anti iodine wine efficiency.
The invention preferably selects the fluorocarbon-containing rubber capsule type reducing agent as a self-made reducing agent, and the fluorocarbon-containing carbon chain capsule type reducing agent is prepared by the following method:
s1: adding an emulsifier into the vitamin C aqueous solution, and adjusting the pH to 2-5 to form an aqueous phase;
s2: mixing hydroxyethyl methacrylate and trimethylolpropane triacrylate to form an oil phase;
s3: mixing the water phase and the oil phase, adding an initiator, stirring to form an emulsion, standing at 80 ℃ in an inert gas atmosphere for reaction, and then performing centrifugal separation, water washing and drying to obtain a solid product A with the surface rich in-OH;
s4: mixing deionized water, a silane coupling agent and ethanol, adjusting the pH value to 3-6, adding a solid product A, stirring and reacting at 60 ℃ under the protection of inert gas, and then carrying out centrifugal separation, water washing and drying to obtain a solid product B with the surface grafted with the silane coupling agent;
s5: mixing the solid product B, a catalyst 1173 and toluene, heating to 50 ℃, dropwise adding perfluoroalkyl mercaptan under the protection of inert gas, irradiating by using an LED lamp with the wavelength of 365nm while stirring, monitoring the reaction through FTIR measurement, after a double bond absorption peak in a reactant disappears, centrifugally separating, washing and drying the reaction solution to obtain the fluorine-containing carbon chain capsule type reducing agent.
The preparation method has simple process, and the prepared reducing agent exists in a capsule manner, which is beneficial to realizing the slow release of the reducing agent, thereby prolonging the action time of the anti-iodine wine effect; by grafting the long fluorocarbon chains on the surfaces of the capsules, the fluorocarbon chain-containing capsule type reducing agent can realize a matte effect without adding matte powder while improving the iodine-proof effect of a paint film, and is multifunctional, so that the improvement of the iodine-proof effect of the paint film is facilitated, and the composition of the matte paint is simplified.
In order to give consideration to the iodine wine resistant effect and the matte effect of the coating, the mass fraction of the vitamin C aqueous solution in the step S1 is preferably 30 percent; preferably, the emulsifier is OP-10, and further preferably, the mass fraction of the emulsifier in the vitamin C aqueous solution is 5%; preferably, the mass ratio of the hydroxyethyl methacrylate to the trimethylolpropane triacrylate in the step S2 is 3: 1; step S3, the mass ratio of the water phase to the oil phase is 1: 5; preferably, the initiator is ABIN, and the initiator accounts for 4% of the mass of the oil phase; preferably, the silane coupling agent in the step S4 is KH570, and further preferably, the mass ratio of the deionized water to the silane coupling agent to the ethanol is 2:1: 5; the volume of the solid product A is 1/4 of the volume of a mixed solution formed by deionized water, a silane coupling agent and ethanol; preferably, the mass-to-volume ratio of the solid product B to the toluene in step S5 is 1:2, i.e., the mass-to-volume ratio of the solid product B to the toluene is 1: 2.
In order to improve the iodine wine resistance of the coating and ensure the mechanical property of the coating, the acrylic resin is preferably selected from at least one of epoxy modified acrylic resin, polyurethane modified acrylic resin, polyester modified acrylic resin and organic silicon modified acrylic resin; the active monomer is at least one selected from pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, 1, 6-ethylene glycol diacrylate and tripropylene glycol diacrylate.
Preferably, the leveling agent is an organic silicon leveling agent; the defoaming agent is an organic silicon defoaming agent or a polyether defoaming agent; the dispersant is a macromolecular dispersant; the initiator is at least one selected from 1-hydroxycyclohexyl phenyl ketone (CBP), 2,4, 6-trimethyl benzoyl diphenoxy phosphorus (TPO) and 4-chlorobenzophenone (184).
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, specific embodiments thereof are described in detail below.
The fluorine-containing carbon chain capsule type reducing agent in each embodiment of the invention is prepared by the following method:
s1: preparing a vitamin C aqueous solution with the mass percentage of 30%, then adding an emulsifier OP-10 into the vitamin C aqueous solution, wherein the mass percentage of the emulsifier in the vitamin C aqueous solution is 5%, and adjusting the pH value of the vitamin C aqueous solution to be 2-5 by using sodium carbonate to form a water phase;
s2: uniformly mixing a mixture of HEMA and TMPTA according to the mass ratio of 3:1 to form an oil phase;
s3: mixing a water phase and an oil phase, adding an initiator ABIN, wherein the mass ratio of the water phase to the oil phase is 1:5, the initiator accounts for 4% of the mass of the oil phase, forming a uniform and stable emulsion under high-speed shearing and stirring, standing and reacting for 10 hours at 80 ℃ in a nitrogen atmosphere, and finally, centrifugally separating, washing and drying the reaction liquid to obtain a solid product A with the surface rich in-OH;
s4: mixing deionized water, KH570 and ethanol in a ratio of 2:1:5 in a three-neck flask, adjusting the pH value to 3-6 with glacial acetic acid, adding a solid product A with the volume of 1/4, stirring for 1 hour at 60 ℃ under the protection of nitrogen, and carrying out centrifugal separation, water washing and drying on reaction liquid to obtain a solid product B with the surface grafted with KH 570;
s5: adding 50g of solid product B, 0.1g of catalyst 1173 and 100mL of toluene into a three-hole round-bottom flask, then raising the temperature of the round-bottom flask to 50 ℃, dropwise adding perfluoroalkyl mercaptan (CAS number: 34451-28-0) accounting for 4% of the mass of the solid product B into the flask under the protection of nitrogen, irradiating the mixture with an LED lamp with the wavelength of 365nm while stirring, monitoring the reaction through FTIR measurement, wherein the double bond absorption peak in the reactant disappears, and obtaining the fluorocarbon chain-containing capsule type reducing agent with the surface grafted with long fluorocarbon chains after centrifugally separating, washing and drying the reaction liquid.
In each example and comparative example of the invention, the organosilicon leveling agent is BYK-333 unless otherwise specified; the dispersing agents are BYK-163; the defoaming agent is BYK-022; the photoinitiators were all 184.
Example 1
The embodiment provides a UV-cured anti-iodine matte coating which comprises the following components in parts by weight:
example 2
The embodiment provides a UV-curable iodine-resistant matte coating which comprises the following components in parts by weight:
example 3
The embodiment provides a UV-cured anti-iodine matte coating which comprises the following components in parts by weight:
example 4
The embodiment provides a UV-curable iodine-resistant matte coating which comprises the following components in parts by weight:
comparative example 1
The comparative example provides a UV-curable iodine-resistant matte coating which comprises the following components in parts by weight:
the self-made capsule type reducing agent is prepared by the following method:
s1: preparing a vitamin C aqueous solution with the mass percentage of 30%, then adding an emulsifier OP-10 into the vitamin C aqueous solution, wherein the mass percentage of the emulsifier in the vitamin C aqueous solution is 5%, and adjusting the pH value of the vitamin C aqueous solution to be 2-5 by using sodium carbonate to form a water phase;
s2: mixing HEMA and TMPTA uniformly according to the mass ratio of 3:1 to form an oil phase;
s3: mixing a water phase and an oil phase, adding an initiator ABIN, wherein the mass ratio of the water phase to the oil phase is 1:5, the initiator accounts for 4% of the oil phase by mass, forming a uniform and stable emulsion under high-speed shearing and stirring, standing and reacting for 10 hours at 80 ℃ in a nitrogen atmosphere, and finally, centrifugally separating, washing and drying the reaction liquid to obtain a solid product A with the surface rich in-OH, wherein the solid product A is the self-made capsule type reducing agent.
Comparative example 2
The comparative example provides a UV-curable iodine-resistant matte coating which comprises the following components in parts by weight:
the leveling agent in the comparative example was a fluorine-containing leveling agent Aifuka 3777.
Comparative example 3
The comparative example provides a UV-curable iodine-resistant matte coating which comprises the following components in parts by weight:
wherein the self-made capsule type reducing agent was prepared according to the method of comparative example 1.
The leveling agent in the comparative example was a fluorine-containing type leveling agent love card 3777.
The paint prepared in each example and comparative example was tested for performance by the following specific test methods:
the coatings prepared in examples 1 to 5 and comparative examples 1 to 2 were applied to glass substrates with UV energy of 600mj/cm 2 The thickness of the film is 10-15 μm.
Iodine resistance: coating iodine tincture on the surface of the cured film, completely drying, wiping with paper towel, and repeating for 50 times; the paint film hardness test is carried out according to GB/T6739-2006; the Baige adhesion test was performed according to GB/T9286-1998; the Martindale test was performed according to BSEN 16094-2012; the wear resistance 100/r test is carried out according to GB/T1768-2006; the gloss (60 ° angle) was measured using a gloss meter; the test results are detailed in table 1.
TABLE 1
The data show that the UV curing iodine-proof paint provided by the invention has excellent iodine-proof performance and matte property on the basis of not increasing matte powder and not damaging the mechanical properties and the like of the paint, and the matte degree of the UV curing iodine-proof paint is even better than that of the paint added with the matte powder in comparative example 2 and comparative example 3.
The coating provided by the comparative example 1 is added with a capsule type reducing agent, but long fluorocarbon chains are not grafted on the reducing agent, so that the obtained coating has good iodine resistance, but cannot show a matte effect; compared with the coating provided by the comparative example 2, the fluorocarbon chain-containing capsule type reducing agent is replaced by matte powder, so that the coating has matte property but no iodine-resistant effect, and the matte property is poor; the coating provided by the comparative example 3 is added with the capsule type reducing agent and the matte powder, but the iodine-wine resistant effect and the matte performance are poorer than those of the coating provided by the embodiment of the invention.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The UV-cured anti-iodine matte coating is characterized by comprising the following components in parts by weight:
2. the UV-curable iodine resistant matte coating of claim 1, wherein said fluorocarbon chain-containing capsule type reducing agent is prepared by the following method:
s1: adding an emulsifier into the vitamin C aqueous solution, and adjusting the pH to 2-5 to form an aqueous phase;
s2: mixing hydroxyethyl methacrylate and trimethylolpropane triacrylate to form an oil phase;
s3: mixing the water phase and the oil phase, adding an initiator, stirring to form an emulsion, standing at 80 ℃ in an inert gas atmosphere for reaction, and then performing centrifugal separation, washing and drying to obtain a solid product A with the surface rich in-OH;
s4: mixing deionized water, a silane coupling agent and ethanol, adjusting the pH value to 3-6, adding the solid product A, stirring and reacting at 60 ℃ under the protection of inert gas, and then carrying out centrifugal separation, washing and drying to obtain a solid product B with the surface grafted with the silane coupling agent;
s5: and mixing the solid product B, a catalyst 1173 and toluene, heating to 50 ℃, adding perfluoroalkyl mercaptan dropwise under the protection of inert gas, stirring and irradiating by using an LED lamp with the wavelength of 365nm, monitoring the reaction by FTIR measurement, and after a double bond absorption peak in a reactant disappears, centrifugally separating, washing and drying the reaction solution to obtain the fluorine-containing carbon chain capsule type reducing agent.
3. The UV-curable iodine alcohol resistant matte coating according to claim 2, wherein the mass fraction of the vitamin C aqueous solution in step S1 is 30%; the mass fraction of the emulsifier in the vitamin C water solution is 5%.
4. The UV-curable iodine alcohol resistant matte paint according to claim 2, wherein the mass ratio of the hydroxyethyl methacrylate to the trimethylolpropane triacrylate in step S2 is 3: 1.
5. The UV-curable iodine alcohol resistant matte coating according to claim 2, wherein the mass ratio of said water phase to said oil phase in step S3 is 1: 5; the initiator accounts for 4% of the mass fraction of the oil phase.
6. The UV-curable iodine alcohol-resistant matte coating as claimed in claim 2, wherein the mass ratio of the deionized water to the silane coupling agent to the ethanol in step S4 is 2:1: 5; the volume of the solid product A is 1/4 of a mixed solution formed by the deionized water, the silane coupling agent and the ethanol.
7. The UV-curable iodine alcohol resistant matte paint according to claim 2, wherein the mass-to-volume ratio of the solid product B to the toluene in step S5 is 1: 2.
8. The UV-curable anti-iodine matte coating according to any one of claims 1-7, wherein said acrylic resin is selected from at least one of epoxy modified acrylic resin, polyurethane modified acrylic resin, polyester modified acrylic resin, silicone modified acrylic resin.
9. The UV-curable iodine alcohol resistant matte coating of claim 8 wherein said reactive monomer is selected from at least one of pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, 1, 6-ethylene glycol diacrylate, tripropylene glycol diacrylate.
10. The UV-curable anti-iodine matte coating according to claim 9, wherein said leveling agent is an organic silicon-based leveling agent; the defoaming agent is an organic silicon defoaming agent or a polyether defoaming agent; the dispersing agent is a macromolecular dispersing agent; the initiator is at least one selected from 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethyl benzoyl diphenylphosphine and 4-chlorobenzophenone.
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| CN115651499B (en) * | 2022-10-26 | 2023-06-23 | 广东希贵光固化材料有限公司 | UV matte coating and application thereof |
| CN115725225A (en) * | 2022-10-31 | 2023-03-03 | 广东希贵光固化材料有限公司 | UVLED (ultraviolet light emitting diode) matte coating and application thereof |
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